Outdoor Atmospheric Micro-/Nanomineral-Mediated Organochlorine Pesticides in Sichuan Basin, China: Adsorption, Occurrence, and Risk Assessment.

Atmospheric micro-/nanominerals play an important role in the adsorption, enrichment, and migration of organochlorine pesticides (OCPs). In the present study, the correlations between OCPs and minerals in outdoor atmospheric dustfall were investigated, and the correlations were used to speculate the source of p,p'-(dicofol+dichlorobenzophenone [DBP]), which is the sum of p,p'-dicofol and p,p'-DBP. Atmospheric dustfall samples were collected from 53 sites in the Chengdu-Deyang-Mianyang economic region in the Sichuan basin. In this region, 24 OCPs were analyzed by gas chromatography-tandem mass spectrometry. The average concentration of 24 OCPs was 51.2 ± 27.4 ng/g. The results showed that the concentration of Σ24 OCPs in urban areas was higher than that in suburban areas (p < 0.05). Minerals in atmospheric dustfall were semiquantitatively analyzed by X-ray diffraction. The primary minerals were quartz, calcite, and gypsum. A Spearman correlation analysis of OCPs and minerals showed that low-volatility OCPs could be adsorbed by minerals in atmospheric dustfall. A density functional theory simulation verified that p,p'-(dicofol+DBP) in atmospheric dustfall was primarily derived from the p,p'-dicofol adsorbed by gypsum. Isomeric ratio results suggested that the samples had weathered lindane and chlordane profiles and confirmed that residents in the Sichuan basin used technical dichlorodiphenyltrichloroethane. Finally, the OCPs were evaluated to determine the potential risk of cancer in adults and children from OCP exposure. Exposure to OCPs via atmospheric dustfall was safe for adults. The cancer risk for children exposed to OCPs was slightly lower than the threshold value (10-6 ) under a high dust ingestion rate, which poses a concern. Environ Toxicol Chem 2023;42:594-604. © 2022 SETAC.

Profiles and determinants of dicofol, endosulfans, mirex, and toxaphenes in breast milk samples from 10 prefectures in Japan.

Human exposure to persistent organic pollutants (POPs) is reflected by POP concentrations in breast milk. Many studies of POPs in breast milk have been performed in Japan, but insufficient information is available about some legacy POPs (e.g., mirex and toxaphenes, included in the Stockholm Convention in 2001) and novel POPs (e.g., dicofol and endosulfans, included in the Stockholm Convention in 2019 and 2011, respectively). In this study, dicofol, endosulfan, mirex, and toxaphene concentrations in breast milk from 10 prefectures in Japan were determined. The samples were collected between 2005 and 2010, before Stockholm Convention restrictions on endosulfans and mirex were implemented. Common POPs (e.g., polychlorinated biphenyls) were also analyzed to allow the contamination statuses to be compared. The α-endosulfan and ß-endosulfan concentrations were 0.26-13 and 0.012-0.82 ng/g lipid, respectively. The toxaphene #26 and #50 concentrations were <0.08-5.6 and < 0.1-8.5 ng/g lipid, respectively. The dicofol concentrations were <0.01-4.8 ng/g lipid. The mirex concentrations were <0.2-3.5 ng/g lipid. The α- and ß-endosulfan concentrations on a lipid weight basis negatively correlated with the lipid contents of the milk samples (ρ = -0.65, p < 0.01 for α-endosulfan; ρ = -0.58, p < 0.01 for ß-endosulfan). The toxaphene concentrations positively correlated with the lipid contents. The mirex concentrations positively correlated with the maternal age but negatively correlated with the maternal body mass index. No correlations between the dicofol concentrations and the factors were found. Principal component analysis divided the data into four groups, (1) chlordanes, dichlorodiphenyltrichloroethanes and related compounds, hexachlorobenzene, hexachlorocyclohexanes, hexachloroethane, and polychlorinated biphenyls, (2) endosulfans, (3) dicofol, dieldrin, and toxaphenes, and (4) bromodiphenyl ether 47. This indicated that bromodiphenyl ether 47, dicofol, endosulfans, and toxaphenes have different exposure routes or different kinetics to the other legacy POPs.

Application of the QuEChERS method for the determination of pesticides, PAHs and PCBs in fish in Senegal.

Pollution of water by persistent organic pollutants is well described; however, little is known about the accumulation of these pollutants by aquatic organisms. For this reason, a method based on QuEChERS extraction and gas chromatography coupled to tandem mass spectrometry (GC-MS/MS) was developed for the determination of pesticides, polychlorinated biphenyls (PCBs) and polycyclic aromatic hydrocarbons (PAHs) in the muscles of five fish species from the bay of Soumbedioune (Dakar, Senegal). This method shows good recoveries of extraction (68.2-98.1% for pesticides, 83.87-98.10% for PAHs and 81.30-98.15% for PCBs), precision (% RSD ≤ 1%), sensitivity (LODs between 0.001 and 0.079 ng g-1), linearity (R2 ≥ 0.99) and repeatability and reproducibility, evaluated for three concentration levels (10 ng g-1, 200 ng g-1 and 500 ng g-1), ≤ 15% for the majority of pollutants under study except for alachlor, atrazine, acetochlor, dicofol, deltamethrin and dichlorvos where a RSD ≥ 20% was determined for the 10 ng g-1 concentration. Organic pollutants have been detected in fish from the Soumbedioune coast demonstrating the necessity of a regular survey of water and fish in order to protect the populations.

Evidence of stockpile contamination for legacy polychlorinated biphenyls and organochlorine pesticides in the urban environment of Cyprus (Eastern Mediterranean): Influence of meteorology on air level variability and gas/particle partitioning based on equilibrium and steady-state models.

The present study investigated comprehensively the atmospheric occurrence and fate of an extensive range of polychlorinated biphenyls (PCBs; forty-two congeners), organochlorine pesticides (OCPs; twenty-seven emerging and legacy agrochemicals) and polycyclic aromatic hydrocarbons (PAHs; fifty parent and alkylated members, including the non USEPA-16 listed toxic ones), in both gas and particulate phase of the scarcely monitored atmosphere over Cyprus for the first time. Parent-metabolite concentration ratios suggested fresh application for dichlorodiphenyl-trichloroethanes (DDTs), dicofol, hexachlorocyclohexanes, endosulfan and chlorothalonil, particularly during spring (April-May). Regressions of logarithms of partial pressure against ambient temperature revealed that secondary recycling from contaminated terrestrial surfaces regulates the atmospheric level variability of PCBs, DDTs, aldrin, chlordane, dicofol, heptachlor and endosulfan. Enthalpies of surface-air exchange (∆HSA) calculated from Clausius-Clapeyron equations were significantly correlated to vaporization enthalpies (∆HV) determined by chromatographic techniques, corroborating presence of potential stockpile-contaminated sites around the study area. The Harner-Bidleman equilibrium model simulating urban areas, and the Li-Jia empirical model, predicted better the partitioning behavior of PAHs (

Assessment of the spatial distribution of organochlorine pesticides (OCPs) and polychlorinated biphenyls (PCBs) in urban soil of China.

Long-term (2004-2018) persistent organic pollutants (POPs) data were collected for urban soils of China. The dataset included concentrations of organochlorine pesticides (OCPs) and polychlorinated biphenyls (PCBs) in soils, comprising a range of different compounds. Understanding the source of OCP and PCB pollution is an important step in controlling and reducing pollution levels in the environment. This study aimed to analyze the spatio-temporal distribution, pollution sources, and potential health risks of OCPs and PCBs in urban soils in different regions of China. It was found that the total OCP concentrations ranged from 7.6 to 37331 µg/kg with a mean value of 2861 µg/kg, and PCBs concentrations ranged from 0.3 to 123467 µg/kg with a mean value of 4984 µg/kg. The highest OCP concentrations were observed in Beijing and Hebei, whereas the highest PCB concentrations were found in the Zhejiang province. The geographical distribution showed that the total mean concentration of POPs of urban soil was much higher in East China than in West China. According to the isomer ratios, about 64% of provinces and cities showed new sources of dichlorodiphenyltrichloroethane (DDT) input and dicofol input was found in 30% of China. Hexachlorocyclohexane (HCH) in urban soils was mainly derived from fresh usage of lindane (γ-HCH) in most regions of China. Lifetime carcinogenic and non-carcinogenic risks of OCPs and PCBs through ingestion, inhalation, and dermal contact indicated that PCBs in urban soils of China often exceeded safe levels. The total lifetime carcinogenic risk values of PCBs were higher than the individual lifetime acceptable risk level (10-4) in 64% of the studied regions and the non-carcinogenic risk values exceeded the target risk level (10-1) in 53% of the regions. The improved knowledge of the distribution and main pollution sources of POPs in urban soil of China as a result of this study can contribute to better decision-making support for soil pollution control and monitoring.

Fates and ecological effects of current-use pesticides (CUPs) in a typical river-estuarine system of Laizhou Bay, North China.

Current-use pesticides (CUPs) are widely applied in agriculture; however, little is known about their environmental behaviors, especially in the freshwater-seawater transitional zone. Water and sediment samples were collected in an intensively human impacted river (Xiaoqing River) from the headwaters to Laizhou Bay to investigate the distributions and environmental fates of four CUPs: trifluralin, chlorothalonil, chlorpyrifos, and dicofol. These CUPs were frequently detected in water and sediment samples. ∑CUPs in water and sediment samples ranged from 1.20 to 100.2 ng L-1 and 6.6-2972.5 ng g-1 dry weight (dw), respectively. Chlorpyrifos and chlorothalonil were the most abundant CUPs in water and sediment samples, respectively. Spatial distribution of CUPs in the Xiaoqing River aquatic ecosystem was mainly influenced by point sources, agricultural activities, the dilution effect by seawater, and environmental parameters. Field-based sediment water partitioning coefficients, normalized by organic carbon (log Koc), were calculated. Interestingly, temperature and salinity exhibited significant impacts on the distribution of log Koc of the four CUPs. The effect of temperature on the distribution of log Koc of the four CUPs varied between the CUPs. In most water samples, the levels of chlorpyrifos exceed the freshwater screening benchmarks. Hence, urgent control measures need to be devised and implemented.

Evaluation of Bayesian approaches to identify DDT source contributions to soils in Southeast China.

Dicofol application may be an important source to elevate the dichlorodiphenyltrichloroethane (DDT) residues to soils in Fujian, Southeast China, after the technical DDT was banned, which left DDT residues from the historical application. The DDT residues varied geographically, corresponding to the varied potential sources of DDT. In this study, a novel approach based on the Bayesian method (BM) was developed to identify the source contributions of DDT to soils, composed with both historical DDT and dicofol. The Naive Bayesian classifier was used basing on the subset of the samples, which were determined by chemical analysis independent of the Bayesian approach. The results show that BM (95%) was higher than that using the ratio of o, p'-/p, p'-DDT (84%) to identify DDT source contributions. High detection rate (97%) of dicofol (p, p'-OH-DDT) was observed in the subset, showing dicofol application influenced the DDX levels in soils in Fujian. However, the contribution from historical technical DDT source was greater than that from dicofol in Fujian, indicating historical technical DDT was still an important pollution source to soils. In addition, both the DDX (DDT isomers and derivatives) level and dicofol contribution in non-agricultural soils were higher than other agricultural land uses, especially in hilly regions, the potential cause may be the atmospheric transport of dicofol type DDT, after spraying during daytime, or regional difference on production and application.

Sources, concentrations and risk factors of organochlorine pesticides in soil, water and sediment in the Yellow River estuary.

The environmental occurrence, sources and risk factors of organochlorine pesticides (HCHs and DDTs) and their isomers or metabolites were studied using comprehensive surveys (including soil, surface water, groundwater and sediment sampling) conducted in the Yellow River Delta (YRD). HCHs and DDTs were all detected in multi environmental media. Compared with reported organochlorine pesticide values in China and abroad and with related environmental quality standards, the concentrations of HCHs and DDTs were generally at low levels in the YRD. Composition of OCPs (DDT metabolites and HCH isomers) showed that DDTs in the multiple environments of the YRD not only came from residues of dicofol but also from atmospheric deposition, while HCH pollution results from the historical usage of a mixture of technical HCH and lindane. Furthermore, the sum of Excess Lifetime Cancer Risk (∑ELCR) exposure to HCHs exceeded the generally acceptable risk level of 1.0E-06 recommended by the USEPA for carcinogenic chemicals.

Global inventory, long-range transport and environmental distribution of dicofol.

The uncertainties on whether dicofol can be identified as a persistent organic pollutant (POP) in terms of its long-range transport (LRT) potential and global distribution, are always a controversial topic during international regulation deliberations. The lack of monitoring data in remote background regions necessitates a model-based evaluation approach for assessing the global distribution of dicofol. However, few model simulations are available at present, as there is no inventory available for global historical usage of dicofol that has sufficiently high spatial and temporal resolution. To describe the current status of global emission, we first developed an inventory of global dicofol usage for the period of 2000-2012 at 1° × 1° latitude/longitude resolution. We then assessed the LRT potential of dicofol by calculating its Arctic Contamination Potential using the Globo-POP model. In addition, we simulated the global mass distribution and the fate of dicofol in the environment using the BETR-Global model at 15° × 15° latitude/longitude resolution. Our estimated inventory established that over the period of 13 years, a total of 28.2 kilo tonnes (kt) of dicofol was applied and released into the environment. East and Southeast Asia, the Mediterranean Coast, and Northern and Central America were identified as hotspots of usage and release. Dicofol exhibited a higher Arctic Contamination Potential than several confirmed Arctic contaminants, and a larger current volume of consumption than most existing POPs. The results of our BETR-Global simulation suggest that (i) dicofol can indeed be transported northward, most likely driven by both atmospheric and oceanic advections from source regions at midlatitudes, and (ii) dicofol will be enriched in remote background regions. Continuous use of dicofol in source regions will result in exposure both locally and in remote regions, and the examination of the potential for adverse effects is therefore of paramount importance. Proactive restrictions at the international level may be warranted.

Feasibility of using terahertz spectroscopy to detect seven different pesticides in wheat flour.

This study investigated the feasibility of detecting pesticides using terahertz (THz) spectroscopy in high-density polyethylene and/or wheat flour mixtures. The absorption spectra of seven pesticides (dicofol, chlorpyrifos, chlorpyrifos-methyl, daminozide, imidacloprid, diethyldithiocarbamate, and dimethyldithiocarbamate) were measured in the frequency range 0.1 to 3 THz at room temperature. Five of the seven pesticides exhibited specific absorption peaks in the low-energy THz range. The two remaining pesticides had no specific absorption peaks in this frequency range, but they exhibited different frequency-dependent refractive indices. The absorption coefficients of imidacloprid increased with its increasing weight ratio in high-density polyethylene, and the fitted power absorptions and refractive indices using a Maxwell-Garnett effective medium model were comparable to the measured data. Imidacloprid was also identified from its characteristic absorption peaks in wheat flour mixtures, and a linear relationship between the absorption coefficient and the weight ratio was observed. Our results show the potential of detection of selected pesticides in foods, such as wheat flour, using THz spectroscopy.

Ionic liquid molecularly imprinted polymers for application in pipette-tip solid-phase extraction coupled with gas chromatography for rapid screening of dicofol in celery.

A new type of ionic liquid molecularly imprinted polymers (IL-MIPs) synthesized by precipitation polymerization using 1-allyl-3-methylimidazolium bromide as an auxiliary solvent and α-chloro-dichlorodiphenyltrichloroethane (α-chloro-DDT) as the template was applied as a selective sorbent of minimized pipette tip-solid-phase extraction (PT-SPE) for rapid isolation and extraction of dicofol (DCF) from celery samples. The pretreatment procedure of celery samples involved only 2.0mg of IL-MIPs, 0.8 mL of acetonitrile-water (ACN-H2O; 1:1, v/v) (washing solvent), and 1.0 mL of acetone-10% acetic acid (HOAc) (elution solvent). Compared with molecularly imprinted polymers (MIPs), ionic liquid-non-imprinted polymers (IL-NIPs) and conventional sorbents such as C18, Si, NH2, and Al2O3-N, IL-MIPs showed higher adsorption and purification capacity to DCF in aqueous solution. Good linearity for DCF was observed in the range from 2.3 to 232.5 ng g(-1) (r(2)=0.9995). The average recoveries at three spiking levels ranged from 86.6% to 101.9% with relative standard deviations (RSDs) of ≤ 6.5% (n=3). The presented IL-MIPs-PT-SPE-GC/ECD method combines the advantages of MIPs, IL, and PT-SPE, and can be used in aqueous conditions with high affinity and selectivity to analytes of complex samples.

Risk assessment of manufacturing equipment surfaces contaminated with DDTs and dicofol.

Decommissioning of manufacturing plant in the chemical industry includes inspection of the surfaces of production equipment for potential contamination and associated health risks. In the present study wipe-samples were taken from the surfaces of dicofol manufacturing equipment at a chemical factory in north China and analyzed for chemicals of concern (COCs). Occupational hygiene assessment was conducted to assess the risks to demolition workers and health risk assessment was performed to evaluate the risks to demolition and general industrial workers. The concentrations of COCs on the equipment surfaces were found to be 0.54-3.75 × 10(4)mg DDTs m(-2) and 0.15-4.38 × 10(3)mg dicofolm(-2). The average concentration of p,p'-DDT does not represent an unacceptable risk to the demolition workers using occupational hygiene assessment. Under the industrial scenario the carcinogenic risks of COCs ranged from 2.28 × 10(-7) to 1.79 × 10(-2) for p,p'-DDT, 6.18 × 10(-7) to 3.04 × 10(-3) for p,p'-DDD and 1.89 × 10(-6) to 0.16 for p,p'-DDE. The non-carcinogenic hazard indices ranged from 3.86 × 10(-3) to 3.03 × 10(2) for p,p'-DDT and 1.16 × 10(-3) to 33.94 for dicofol. Both carcinogenic risk and hazard index of COCs under the industrial scenario were higher than under the demolition scenario. Oral ingestion and dermal contact were the major pathways and accounted for >88% of the total exposure of COCs. Parameter sensitivity analysis shows that equipment surface concentration (Cs), frequency of contact with surface (EV), fraction of dust transferred from surface to skin (FTss) and exposure frequency (EF) were the most sensitive parameters and these should be acquired on a site-specific basis. The accuracy of the risk assessment was controlled largely by the variation in the sensitive parameters and the uncertainty of the exposure model for the inhalation pathway.

The release of persistent organic pollutants from a closed system dicofol production process.

High concentrations of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) have been found to be produced in chemical processes in which chlorine is a raw material. Samples of workshop air, waste water, waste acid, and the dicofol product were collected from a pesticide factory in China that uses a closed-system dicofol production process, and were analyzed for PCDD/Fs and ΣDDTs. The ΣDDTs concentrations were 1.88-17.53 µg m(-3) in the workshop air samples, 4.85-456 µg kg(-1) in the waste water and waste acid samples, and 4.74 g kg(-1) in the dicofol product. The total estimated daily intakes of ΣDDTs for workers by inhalation in the workplace were in the range of 0.38-3.51 µg kg(-1)bwd(-1) for moderate activities. The annual amounts of ΣDDTs and p,p'-DDT directly released to the environment via the use of dicofol were 9,480 kg and 1,080 kg, respectively. The PCDD/F toxicity equivalent values (I-TEQs) in the waste water and waste acid samples ranged from 1.5 to 122 pg I-TEQ kg(-1) and 86.3 ng I-TEQ kg(-1) in the dicofol sample. The annual amount of PCDD/Fs released to the environment was 0.17 g I-TEQ. From the PCDD/F distribution patterns, it is suggested that the major pathway for PCDD/F formation involves precursor synthesis during the production of dicofol in the closed-system process.

Ionic liquid-mediated molecularly imprinted solid-phase extraction coupled with gas chromatography-electron capture detector for rapid screening of dicofol in vegetables.

New ionic liquid-mediated molecularly imprinted polymers (IL-MIPs) were prepared by precipitation polymerization using 1-butyl-3-methylimidazolium hexafluorophosphate (BMIM(+)PF6(-)) as the auxiliary solvent, α-chloro-DDT as the dummy template, and they were successfully applied as the sorbents of solid-phase extraction (SPE) for rapid screening of dicofol from cabbage, tomato, and carrot samples. The IL-MIPs were characterized by FTIR, FE-SEM, static adsorption and chromatographic evaluation, and the results revealed that the IL-MIPs had higher adsorption capacity and selectivity to dicofol in aqueous solution than that of ionic liquid-mediated non-imprinted polymers (IL-NIPs) and non-imprinted polymers (NIPs). Under the optimized conditions, the IL-MIPs-SPE-GC method offered good linearity (0.4-40.0ngg(-1), r(2)=0.9995) and the average recoveries of dicofol at three spiked levels were in a range of 84.6-104.1% (n=3) with RSD≤7.6%. The proposed method obviously improved the selectivity and purification effect, and eliminated the effect of template leakage on dicofol quantitative analysis.

Characteristics of DDTs in fish from Lake Taihu: an indicator of continual DDTs input in China.

Four typical freshwater fish species in Lake Taihu (TH), China, were collected and analyzed for the residue levels of DDT and its metabolites DDD and DDE (sum of o,p'- and p,p'-DDT, DDD, and DDE is designated as DDTs). The DDTs concentrations ranged from 3.24 to 37.1 ng/g, and p,p'-DDE was the dominant isomer, followed by p,p'-DDD and o,p'-DDT. Source identification indicated that DDTs in TH was mostly stemmed from the historical usage of technical DDT mixture, but a new source of DDT, i.e., dicofol-type DDT, also occurred. The results from the present work, together with previously published data, clearly indicate that dicofol-type DDT was widespread and was an important continual source of DDTs in China.

Organochlorine pesticides in soil under irrigated cotton farming systems in Vertisols of the Namoi Valley, north-western New South Wales, Australia.

Organochlorine pesticides (OCPs) such as DDT and DDE have been detected in the surface 0.2m of Vertisols in the lower Namoi Valley of north western New South Wales, Australia even though they have not been applied to crops since 1982. However, their presence in the deeper soil horizons has not been investigated. The objective of this study was to determine if OCPs were present to a depth of 1.2m in Vertisols under irrigated cotton farming systems in the lower Namoi Valley of New South Wales. Soil was sampled from the 0-1.2m depths in three sites, viz. the Australian Cotton Research Institute, ACRI, near Narrabri (149°36'E, 30°12'S), and two cotton farms near Wee Waa (149°27'E, 30°13'S) and Merah North (149°18'E, 30°12'S) in northern New South Wales, Australia. The OCPs detected and their metabolites were α-endosulfan, ß-endosulfan, endosulfan sulphate, DDD, DDE, DDT and endrin. The metabolite DDE, a breakdown product of DDT, was the most persistent OCP in all depths analysed. Endosulfan sulphate was the second most persistent followed by endrin>α-endosulfan>ß-endosulfan>DDT and DDD. DDT was sprayed extensively in the lower Namoi Valley up to the early 1980s and may explain the persistence of DDE in the majority of soil samples. Dicofol and Dieldrin, two OCPs previously undocumented in Vertisols were also detected. The movement of OCPs into the subsoil of Vertisols may occur when irrigation or rain transports soil colloids and organic matter via preferential flow systems into the deeper layers of a soil profile. Persistence of OCPs was closely correlated to soil organic carbon concentrations. The persistence in soil of OCP's applied to cotton crops grown more than two decades ago suggests that they could enter the food chain. Their presence at depths of 1.2m suggests that they could move into groundwater that may eventually be used for domestic and stock consumption.

Pesticide residues in tomatoes from greenhouses in Souss Massa Valley, Morocco.

Eight pesticide residues in tomato samples collected in the area of Souss Massa Valley (Southern Morocco) were analyzed. The detected residue levels ranged from 0.001 to 0.400 mg kg(-1) for dicofol, from 0.003 to 0.170 mg kg(-1) for procymidone, from 0.001 to 0.250 mg kg(-1) for chlorothalonil, from 0.050 to 0.500 mg kg(-1) for bifenthrin, from 0.001 to 0.010 mg kg(-1) for λ-cyhalothrin, from 0.001 to 0.300 mg kg(-1) for cypermethrin, from 0.010 to 1 mg kg(-1) for deltamethrin and from 0.003 to 1.123 mg kg(-1) for endosulfan. European MRL for endosulfan in tomatoes set in 0.500 mg kg(-1), was exceeded in 8 samples, and MRL for deltamethrin set in 0.300 mg kg(-1) for tomatoes was exceeded in 2 samples.

Determination of dicofol in aquatic products using molecularly imprinted solid-phase extraction coupled with GC-ECD detection.

The novel molecularly imprinted microsphere (MIM) that could be applied as special sorbent was synthesized by aqueous suspension polymerization using 1,1-bis(4-chlorophenyl)-1,2,2,2-tetrachloroethane (α-chloro-DDT) as the dummy template. The obtained MIM exhibited good recognition and selectivity to dicofol and it was successfully applied as selective sorbent of solid-phase extraction for the determination of dicofol from aquatic products. At the optimum conditions of the molecularly imprinted solid-phase extraction (MISPE) coupled with GC-ECD, good linearity for dicofol was achieved in a range of 0.4-100 ng g(-1) (r(2)=0.9995) and the recoveries at three spiked levels were ranged from 85.8% to 101.2% for aquatic products with the relative standard deviation (RSD) less than 5.6%. The presented MISPE-GC-ECD method exhibited the advantages of simplicity, selectivity and sensitivity, and could be potentially applied to the determination of dicofol in complicated aquatic products.

Determination of n-octanol/water partition coefficient for DDT-related compounds by RP-HPLC with a novel dual-point retention time correction.

n-Octanol/water partition coefficients (P) for DDTs and dicofol were determined by reversed-phase high performance liquid chromatography (RP-HPLC) on a C(18) column using methanol-water mixture as mobile phase. A dual-point retention time correction (DP-RTC) was proposed to rectify chromatographic retention time (t(R)) shift resulted from stationary phase aging. Based on this correction, the relationship between logP and logk(w), the logarithm of the retention factor extrapolated to pure water, was investigated for a set of 12 benzene homologues and DDT-related compounds with reliable experimental P as model compounds. A linear regression logP=(1.10±0.04) logk(w) - (0.60±0.17) was established with correlation coefficient R(2) of 0.988, cross-validated correlation coefficient R(cv)(2) of 0.983 and standard deviation (SD) of 0.156. This model was further validated using four verification compounds, naphthalene, biphenyl, 2,2-bis(4-chlorophenyl)-1,1-dichloroethane (p,p'-DDD) and 2,2-bis(4-chlorophenyl)-1,1-dichloroethene (p,p'-DDE) with similar structure to DDT. The RP-HPLC-determined P values showed good consistency with shake-flask (SFM) or slow-stirring (SSM) results, especially for highly hydrophobic compounds with logP in the range of 4-7. Then, the P values for five DDT-related compounds, 2-(2-chlorophenyl)-2-(4-chlorophenyl)-1,1,1-trichloroethane (o,p'-DDT), 2-(2-chlorophenyl)-2-(4-chlorophenyl)-1,1-dichloroethane (o,p'-DDD), 2-(2-chlorophenyl)-2-(4-chlorophenyl)-1,1-dichloroethene (o,p'-DDE), and 2,2,2-trichloro-1,1-bis(4-chlorophenyl)ethanol (dicofol) and its main degradation product 4,4'-dichlorobenzophenone (p,p'-DBP) were evaluated by the improved RP-HPLC method for the first time. The excellent precision with SD less than 0.03 proved that the novel DP-RTC protocol can significantly increases the determination accuracy and reliability of P by RP-HPLC.

Persistence of dicofol residues in cotton lint seed, and soil.

A supervised field trial was conducted at the CCS Haryana Agricultural University, Hisar to assess the residues of dicofol on cotton, during Kharif season, 2008. Dicofol (Kelthane 18.5EC) was applied at 500 g a.i./ha (T(1)) and 1,000 g a.i./ha T(2)) after 105 days of sowing of cotton crop (Varity Cotton/H-1226). Soil samples were collected on 0 (1 h after treatment), 3, 7, 10, 15, 30, and 60 days after spray and cotton samples were collected at harvest. Samples were processed and residues were quantified by GC-ECD system equipped with capillary column. Limit of detection and limit of quantification (LOQ) were 0.001 and 0.010 mg kg( -1), respectively, for soil and LOQ for cotton lint and seed was 0.020 mg kg( -1). Initial residues of 0.588 and 1.182 mg kg( -1) in soil reached below detectable level (BDL) of 0.010 mg kg( -1) in T(1) and to the level of BDL (0.010 mg kg( -1)) in T(2) at harvest (60 days after treatment). In 60 days, residues dissipated almost completely (100 and >99%) in both the treatments. Half-life period was calculated as 8.57 days at single dose and 8.69 days at double dose in soil. Residues of dicofol were detected in cotton lint to the levels of 0.292 and 0.653 mg kg( -1) and in seed 0.051 and 0.090 mg kg( -1) in T(1) and T(2) doses, respectively at harvest. Residues in cotton seed were below MRL value of 0.01 mg kg( -1) in both the doses.